Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028371/hy2066sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028371/hy2066Isup2.hkl |
CCDC reference: 654763
Key indicators
- Single-crystal X-ray study
- T = 213 K
- Mean (C-C) = 0.007 Å
- R factor = 0.042
- wR factor = 0.094
- Data-to-parameter ratio = 14.2
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) ... 4.00 Ratio
Alert level C PLAT213_ALERT_2_C Atom C7 has ADP max/min Ratio ............. 3.40 prola PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.94 Ratio PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - C11 .. 5.79 su PLAT318_ALERT_2_C Check Hybridisation of N12 in Main Residue . ? PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C2 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C3 PLAT412_ALERT_2_C Short Intra XH3 .. XHn H2A .. H14A .. 1.81 Ang. PLAT412_ALERT_2_C Short Intra XH3 .. XHn H3A .. H22A .. 1.80 Ang. PLAT420_ALERT_2_C D-H Without Acceptor N12 - H12B ... ?
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of N1 = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of N5 = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of N9 = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of N11 = ... R PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni2 (2) 1.90 PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni3 (2) 1.89
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 7 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
Compound (I) was obtained by adding 2 equivalents of CH3Li (2 mmol) to deprotonate a THF solution (15 ml) of the organic amine, 2,6-dimethylaminopyridine (0.137 g, 1 mmol), at 195 K. This mixture was then transferred via cannula to solid, anhydrous NiCl2 (0.130 g, 1 mmol). After stirring the mixture at room temperature for 5 h, the solvent was removed under vacuum. The brown solid was extracted with CH2Cl2 (10 ml). To this solution was added a layer of hexanes (30 ml). After a week at room temperature, large block-shaped, deep brown crystals were isolated.
All H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.94 Å (CH) and 0.97 Å (CH3), Uiso(H) = 1.2Ueq(C) and 1.5Ueq(C), and N—H = 0.87 Å, Uiso(H) = 1.2Ueq(N).
Molecules in the title complex, (I) (Fig. 1), are non-centrosymmetic but the crystals are racemic. During the reaction, two equivalents of the organic amine were fully deprotonated forming dianions and two equivalents were only partially deprotonated giving monoanions. In this tetranuclear complex, there are four divalent Ni atoms. Two of them, Ni1 and Ni4, are square planar and bonded to four N donors while the others, Ni2 and Ni3, are in a distorted tetrahedral geometry, with three coordination sites occupied by N donors and the fourth one by a Cl atom (Table 1). Even though there are a series of compounds having three Ni atoms forming a linear chain that have both four-coordinate and five-coordinate metal atoms (Clérac et al., 1999; Cotton et al., 2001, 2006), examples of clusters having four Ni atoms in a four-coordinate environment but two different geometries are rare.
For related structures, see: Clérac et al. (1999); Cotton et al. (2001, 2006).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 40% probability level. H atoms have been omitted for clarity. | |
Fig. 2. The packing diagram of (I). |
[Ni4(C7H9N3)2(C7H10N3)2Cl2] | F(000) = 1744 |
Mr = 848.44 | Dx = 1.669 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5894 reflections |
a = 12.710 (7) Å | θ = 2.5–25.0° |
b = 10.903 (6) Å | µ = 2.40 mm−1 |
c = 24.729 (14) Å | T = 213 K |
β = 99.842 (11)° | Block, brown |
V = 3376 (3) Å3 | 0.38 × 0.10 × 0.10 mm |
Z = 4 |
Bruker SMART 1000 area-detector diffractometer | 5894 independent reflections |
Radiation source: fine-focus sealed tube | 4026 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
φ and ω scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→15 |
Tmin = 0.463, Tmax = 0.796 | k = −12→9 |
16834 measured reflections | l = −29→29 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.042 | w = 1/[σ2(Fo2) + (0.033P)2 + 0.98P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.094 | (Δ/σ)max = 0.001 |
S = 1.08 | Δρmax = 0.66 e Å−3 |
5894 reflections | Δρmin = −0.58 e Å−3 |
415 parameters |
[Ni4(C7H9N3)2(C7H10N3)2Cl2] | V = 3376 (3) Å3 |
Mr = 848.44 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.710 (7) Å | µ = 2.40 mm−1 |
b = 10.903 (6) Å | T = 213 K |
c = 24.729 (14) Å | 0.38 × 0.10 × 0.10 mm |
β = 99.842 (11)° |
Bruker SMART 1000 area-detector diffractometer | 5894 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4026 reflections with I > 2σ(I) |
Tmin = 0.463, Tmax = 0.796 | Rint = 0.057 |
16834 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.66 e Å−3 |
5894 reflections | Δρmin = −0.58 e Å−3 |
415 parameters |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.85881 (5) | 0.60891 (5) | 0.15069 (2) | 0.02005 (16) | |
Ni2 | 0.69244 (5) | 0.44549 (6) | 0.08446 (2) | 0.02496 (17) | |
Ni3 | 0.78862 (5) | 0.84198 (6) | 0.22024 (2) | 0.02465 (17) | |
Ni4 | 0.68609 (5) | 0.74121 (6) | 0.11001 (2) | 0.02360 (16) | |
Cl1 | 0.69651 (12) | 0.30291 (14) | 0.01981 (6) | 0.0501 (4) | |
Cl2 | 0.82948 (11) | 1.02671 (12) | 0.25863 (6) | 0.0431 (4) | |
N9 | 0.7045 (3) | 0.6199 (3) | 0.05452 (14) | 0.0229 (9) | |
N1 | 0.8208 (3) | 0.4386 (4) | 0.14373 (14) | 0.0236 (9) | |
N6 | 0.5910 (3) | 0.6543 (4) | 0.14663 (15) | 0.0275 (10) | |
N11 | 0.8911 (3) | 0.7805 (3) | 0.17005 (14) | 0.0214 (9) | |
N8 | 0.8902 (3) | 0.6215 (3) | 0.07831 (14) | 0.0211 (9) | |
N5 | 0.6492 (3) | 0.8413 (4) | 0.16761 (15) | 0.0265 (10) | |
C12 | 0.7661 (4) | 0.3467 (5) | 0.22874 (18) | 0.0266 (11) | |
H12A | 0.7598 | 0.2651 | 0.2163 | 0.032* | |
C45 | 0.8823 (4) | 0.8608 (4) | 0.12564 (19) | 0.0244 (11) | |
C35 | 0.8042 (4) | 0.6318 (4) | 0.03666 (18) | 0.0211 (11) | |
N3 | 0.7878 (3) | 0.7147 (4) | 0.27437 (15) | 0.0281 (10) | |
C41 | 0.7679 (4) | 0.9352 (5) | 0.0482 (2) | 0.0342 (13) | |
C15 | 0.7818 (4) | 0.5948 (5) | 0.26349 (18) | 0.0261 (12) | |
C31 | 0.9908 (4) | 0.6291 (4) | 0.06617 (18) | 0.0224 (11) | |
C34 | 0.8177 (4) | 0.6542 (4) | −0.01643 (18) | 0.0271 (12) | |
H34A | 0.7584 | 0.6600 | −0.0448 | 0.033* | |
N7 | 1.0728 (3) | 0.6098 (4) | 0.10788 (15) | 0.0282 (10) | |
H7A | 1.0583 | 0.5847 | 0.1392 | 0.034* | |
N2 | 0.8066 (3) | 0.5571 (4) | 0.21415 (14) | 0.0224 (9) | |
N10 | 0.7866 (3) | 0.8578 (3) | 0.09147 (15) | 0.0247 (9) | |
C33 | 0.9199 (4) | 0.6679 (5) | −0.02711 (19) | 0.0313 (13) | |
H33A | 0.9297 | 0.6859 | −0.0631 | 0.038* | |
C1 | 0.8999 (4) | 0.3439 (5) | 0.1353 (2) | 0.0347 (13) | |
H1A | 0.9595 | 0.3461 | 0.1655 | 0.052* | |
H1B | 0.9255 | 0.3600 | 0.1012 | 0.052* | |
H1C | 0.8666 | 0.2637 | 0.1335 | 0.052* | |
C4 | 0.6031 (4) | 0.9650 (5) | 0.1564 (2) | 0.0421 (15) | |
H4A | 0.5362 | 0.9588 | 0.1310 | 0.063* | |
H4B | 0.6525 | 1.0158 | 0.1405 | 0.063* | |
H4C | 0.5902 | 1.0016 | 0.1905 | 0.063* | |
C8 | 0.9947 (3) | 0.7864 (4) | 0.20777 (19) | 0.0271 (12) | |
H8A | 1.0512 | 0.7592 | 0.1887 | 0.041* | |
H8B | 0.9924 | 0.7338 | 0.2392 | 0.041* | |
H8C | 1.0084 | 0.8702 | 0.2202 | 0.041* | |
C6 | 0.6110 (4) | 0.6238 (5) | 0.00933 (18) | 0.0300 (12) | |
H6A | 0.6078 | 0.7032 | −0.0086 | 0.045* | |
H6B | 0.5461 | 0.6107 | 0.0242 | 0.045* | |
H6C | 0.6180 | 0.5600 | −0.0172 | 0.045* | |
C21 | 0.5402 (4) | 0.5453 (5) | 0.14940 (18) | 0.0263 (11) | |
C13 | 0.7460 (4) | 0.3815 (5) | 0.28017 (19) | 0.0308 (13) | |
H13A | 0.7270 | 0.3209 | 0.3037 | 0.037* | |
C32 | 1.0067 (4) | 0.6562 (5) | 0.01277 (18) | 0.0291 (12) | |
H32A | 1.0759 | 0.6660 | 0.0048 | 0.035* | |
C22 | 0.4607 (4) | 0.5417 (5) | 0.18400 (19) | 0.0325 (13) | |
H22A | 0.4211 | 0.4698 | 0.1866 | 0.039* | |
C42 | 0.8451 (5) | 1.0147 (5) | 0.0362 (2) | 0.0456 (15) | |
H42A | 0.8312 | 1.0669 | 0.0056 | 0.055* | |
C11 | 0.7955 (3) | 0.4397 (5) | 0.19779 (18) | 0.0231 (11) | |
N4 | 0.5677 (3) | 0.4520 (4) | 0.12021 (15) | 0.0271 (10) | |
C25 | 0.5747 (4) | 0.7504 (5) | 0.17780 (19) | 0.0301 (12) | |
C14 | 0.7529 (4) | 0.4998 (5) | 0.29750 (19) | 0.0312 (13) | |
H14A | 0.7383 | 0.5192 | 0.3325 | 0.037* | |
C5 | 1.1831 (4) | 0.6287 (5) | 0.1031 (2) | 0.0371 (14) | |
H5A | 1.2283 | 0.6097 | 0.1378 | 0.056* | |
H5B | 1.1937 | 0.7136 | 0.0936 | 0.056* | |
H5C | 1.2016 | 0.5755 | 0.0747 | 0.056* | |
C2 | 0.7635 (5) | 0.7497 (5) | 0.32769 (19) | 0.0450 (15) | |
H2A | 0.7660 | 0.6777 | 0.3509 | 0.068* | |
H2B | 0.6927 | 0.7856 | 0.3230 | 0.068* | |
H2C | 0.8156 | 0.8092 | 0.3447 | 0.068* | |
C23 | 0.4429 (4) | 0.6434 (6) | 0.2131 (2) | 0.0408 (15) | |
H23A | 0.3897 | 0.6401 | 0.2352 | 0.049* | |
C44 | 0.9628 (4) | 0.9405 (5) | 0.1151 (2) | 0.0347 (13) | |
H44A | 1.0294 | 0.9425 | 0.1385 | 0.042* | |
C24 | 0.5000 (4) | 0.7520 (5) | 0.2116 (2) | 0.0372 (14) | |
H24A | 0.4881 | 0.8213 | 0.2323 | 0.045* | |
C7 | 0.6361 (6) | 0.9856 (6) | −0.0350 (2) | 0.084 (3) | |
H7B | 0.5610 | 0.9703 | −0.0486 | 0.126* | |
H7C | 0.6786 | 0.9510 | −0.0603 | 0.126* | |
H7D | 0.6485 | 1.0733 | −0.0319 | 0.126* | |
N12 | 0.6660 (4) | 0.9295 (4) | 0.01813 (18) | 0.0474 (13) | |
H12B | 0.6174 | 0.8900 | 0.0320 | 0.057* | |
C3 | 0.5172 (4) | 0.3343 (5) | 0.1267 (2) | 0.0370 (13) | |
H3A | 0.4560 | 0.3464 | 0.1448 | 0.055* | |
H3B | 0.5680 | 0.2802 | 0.1487 | 0.055* | |
H3C | 0.4938 | 0.2977 | 0.0909 | 0.055* | |
C43 | 0.9424 (5) | 1.0160 (5) | 0.0698 (2) | 0.0478 (16) | |
H43A | 0.9961 | 1.0690 | 0.0619 | 0.057* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0208 (3) | 0.0221 (4) | 0.0173 (3) | −0.0009 (3) | 0.0035 (2) | −0.0001 (3) |
Ni2 | 0.0246 (3) | 0.0261 (4) | 0.0238 (3) | −0.0024 (3) | 0.0032 (3) | −0.0022 (3) |
Ni3 | 0.0248 (3) | 0.0252 (4) | 0.0231 (3) | 0.0019 (3) | 0.0016 (3) | −0.0030 (3) |
Ni4 | 0.0203 (3) | 0.0264 (4) | 0.0230 (3) | 0.0010 (3) | 0.0007 (3) | −0.0012 (3) |
Cl1 | 0.0583 (9) | 0.0478 (10) | 0.0442 (8) | 0.0032 (8) | 0.0088 (7) | −0.0205 (7) |
Cl2 | 0.0510 (9) | 0.0275 (8) | 0.0484 (8) | −0.0018 (7) | 0.0018 (7) | −0.0116 (6) |
N9 | 0.022 (2) | 0.025 (2) | 0.021 (2) | −0.002 (2) | 0.0005 (17) | −0.0003 (17) |
N1 | 0.023 (2) | 0.026 (2) | 0.022 (2) | −0.002 (2) | 0.0049 (17) | −0.0030 (18) |
N6 | 0.022 (2) | 0.037 (3) | 0.022 (2) | 0.001 (2) | 0.0009 (17) | −0.0017 (19) |
N11 | 0.023 (2) | 0.021 (2) | 0.020 (2) | 0.0011 (19) | 0.0014 (16) | 0.0014 (17) |
N8 | 0.025 (2) | 0.023 (2) | 0.016 (2) | −0.0025 (19) | 0.0048 (17) | −0.0027 (16) |
N5 | 0.024 (2) | 0.029 (2) | 0.025 (2) | 0.003 (2) | 0.0012 (18) | −0.0068 (19) |
C12 | 0.027 (3) | 0.022 (3) | 0.030 (3) | −0.005 (2) | 0.000 (2) | 0.007 (2) |
C45 | 0.029 (3) | 0.016 (3) | 0.028 (3) | 0.002 (2) | 0.005 (2) | −0.002 (2) |
C35 | 0.025 (3) | 0.016 (3) | 0.022 (2) | −0.001 (2) | 0.004 (2) | −0.003 (2) |
N3 | 0.035 (2) | 0.029 (3) | 0.023 (2) | 0.002 (2) | 0.0104 (19) | −0.0047 (19) |
C41 | 0.046 (3) | 0.023 (3) | 0.031 (3) | 0.004 (3) | 0.001 (3) | 0.005 (2) |
C15 | 0.020 (2) | 0.040 (4) | 0.017 (2) | 0.005 (3) | 0.001 (2) | 0.004 (2) |
C31 | 0.026 (3) | 0.019 (3) | 0.024 (3) | −0.001 (2) | 0.008 (2) | −0.001 (2) |
C34 | 0.033 (3) | 0.029 (3) | 0.019 (3) | 0.000 (3) | 0.003 (2) | 0.004 (2) |
N7 | 0.018 (2) | 0.043 (3) | 0.025 (2) | −0.001 (2) | 0.0056 (17) | 0.002 (2) |
N2 | 0.024 (2) | 0.025 (2) | 0.019 (2) | 0.002 (2) | 0.0069 (17) | 0.0009 (18) |
N10 | 0.027 (2) | 0.019 (2) | 0.027 (2) | 0.005 (2) | −0.0003 (18) | 0.0015 (18) |
C33 | 0.041 (3) | 0.035 (3) | 0.020 (3) | −0.004 (3) | 0.012 (2) | 0.004 (2) |
C1 | 0.034 (3) | 0.038 (3) | 0.034 (3) | 0.008 (3) | 0.009 (2) | −0.003 (3) |
C4 | 0.042 (3) | 0.043 (4) | 0.037 (3) | 0.015 (3) | −0.004 (3) | −0.006 (3) |
C8 | 0.020 (2) | 0.028 (3) | 0.031 (3) | −0.001 (2) | −0.003 (2) | −0.002 (2) |
C6 | 0.029 (3) | 0.035 (3) | 0.024 (3) | −0.003 (3) | −0.002 (2) | −0.001 (2) |
C21 | 0.020 (3) | 0.035 (3) | 0.022 (3) | −0.003 (3) | −0.002 (2) | −0.001 (2) |
C13 | 0.026 (3) | 0.038 (4) | 0.027 (3) | −0.003 (3) | 0.000 (2) | 0.017 (2) |
C32 | 0.031 (3) | 0.032 (3) | 0.027 (3) | −0.004 (3) | 0.012 (2) | 0.000 (2) |
C22 | 0.017 (3) | 0.047 (4) | 0.033 (3) | 0.000 (3) | 0.006 (2) | 0.005 (3) |
C42 | 0.070 (4) | 0.030 (3) | 0.036 (3) | −0.003 (3) | 0.007 (3) | 0.012 (3) |
C11 | 0.013 (2) | 0.033 (3) | 0.022 (2) | 0.006 (2) | −0.0010 (19) | −0.001 (2) |
N4 | 0.024 (2) | 0.028 (3) | 0.029 (2) | −0.005 (2) | 0.0031 (18) | 0.000 (2) |
C25 | 0.023 (3) | 0.039 (3) | 0.028 (3) | 0.002 (3) | 0.001 (2) | −0.002 (2) |
C14 | 0.029 (3) | 0.043 (4) | 0.022 (3) | 0.003 (3) | 0.007 (2) | 0.007 (2) |
C5 | 0.024 (3) | 0.055 (4) | 0.032 (3) | −0.001 (3) | 0.006 (2) | −0.002 (3) |
C2 | 0.065 (4) | 0.045 (4) | 0.027 (3) | 0.006 (3) | 0.016 (3) | −0.003 (3) |
C23 | 0.026 (3) | 0.070 (4) | 0.030 (3) | 0.008 (3) | 0.015 (2) | 0.003 (3) |
C44 | 0.029 (3) | 0.031 (3) | 0.045 (3) | −0.008 (3) | 0.009 (2) | 0.002 (3) |
C24 | 0.025 (3) | 0.052 (4) | 0.036 (3) | 0.008 (3) | 0.007 (2) | −0.004 (3) |
C7 | 0.127 (7) | 0.061 (5) | 0.043 (4) | −0.002 (5) | −0.045 (4) | 0.020 (3) |
N12 | 0.055 (3) | 0.041 (3) | 0.040 (3) | 0.002 (3) | −0.012 (2) | 0.013 (2) |
C3 | 0.037 (3) | 0.045 (4) | 0.030 (3) | −0.010 (3) | 0.007 (2) | 0.001 (3) |
C43 | 0.052 (4) | 0.032 (4) | 0.063 (4) | −0.017 (3) | 0.022 (3) | 0.006 (3) |
Ni1—N2 | 1.891 (4) | N7—H7A | 0.8700 |
Ni1—N8 | 1.904 (4) | N2—C11 | 1.343 (6) |
Ni1—N1 | 1.919 (4) | C33—C32 | 1.354 (6) |
Ni1—N11 | 1.957 (4) | C33—H33A | 0.9400 |
Ni1—C11 | 2.393 (5) | C1—H1A | 0.9700 |
Ni1—Ni4 | 2.6753 (14) | C1—H1B | 0.9700 |
Ni2—N4 | 1.945 (4) | C1—H1C | 0.9700 |
Ni2—N1 | 2.000 (4) | C4—H4A | 0.9700 |
Ni2—N9 | 2.056 (4) | C4—H4B | 0.9700 |
Ni2—Cl1 | 2.2369 (17) | C4—H4C | 0.9700 |
Ni3—N3 | 1.929 (4) | C8—H8A | 0.9700 |
Ni3—N5 | 2.012 (4) | C8—H8B | 0.9700 |
Ni3—N11 | 2.059 (4) | C8—H8C | 0.9700 |
Ni3—Cl2 | 2.2492 (18) | C6—H6A | 0.9700 |
Ni4—N6 | 1.885 (4) | C6—H6B | 0.9700 |
Ni4—N10 | 1.913 (4) | C6—H6C | 0.9700 |
Ni4—N5 | 1.915 (4) | C21—N4 | 1.328 (6) |
Ni4—N9 | 1.948 (4) | C21—C22 | 1.432 (6) |
Ni4—C25 | 2.374 (5) | C13—C14 | 1.357 (7) |
N9—C35 | 1.417 (5) | C13—H13A | 0.9400 |
N9—C6 | 1.487 (5) | C32—H32A | 0.9400 |
N1—C11 | 1.427 (5) | C22—C23 | 1.362 (7) |
N1—C1 | 1.480 (6) | C22—H22A | 0.9400 |
N6—C25 | 1.337 (6) | C42—C43 | 1.366 (8) |
N6—C21 | 1.360 (6) | C42—H42A | 0.9400 |
N11—C45 | 1.394 (6) | N4—C3 | 1.456 (6) |
N11—C8 | 1.479 (5) | C25—C24 | 1.369 (6) |
N8—C31 | 1.365 (5) | C14—H14A | 0.9400 |
N8—C35 | 1.372 (5) | C5—H5A | 0.9700 |
N5—C25 | 1.423 (6) | C5—H5B | 0.9700 |
N5—C4 | 1.478 (6) | C5—H5C | 0.9700 |
C12—C11 | 1.361 (6) | C2—H2A | 0.9700 |
C12—C13 | 1.392 (6) | C2—H2B | 0.9700 |
C12—H12A | 0.9400 | C2—H2C | 0.9700 |
C45—N10 | 1.357 (6) | C23—C24 | 1.393 (7) |
C45—C44 | 1.401 (6) | C23—H23A | 0.9400 |
C35—C34 | 1.375 (6) | C44—C43 | 1.378 (7) |
N3—C15 | 1.334 (6) | C44—H44A | 0.9400 |
N3—C2 | 1.456 (5) | C24—H24A | 0.9400 |
C41—N10 | 1.352 (6) | C7—N12 | 1.440 (7) |
C41—N12 | 1.379 (6) | C7—H7B | 0.9700 |
C41—C42 | 1.379 (7) | C7—H7C | 0.9700 |
C15—N2 | 1.374 (5) | C7—H7D | 0.9700 |
C15—C14 | 1.422 (6) | N12—H12B | 0.8700 |
C31—N7 | 1.352 (6) | C3—H3A | 0.9700 |
C31—C32 | 1.401 (6) | C3—H3B | 0.9700 |
C34—C33 | 1.377 (6) | C3—H3C | 0.9700 |
C34—H34A | 0.9400 | C43—H43A | 0.9400 |
N7—C5 | 1.442 (5) | ||
N2—Ni1—N8 | 163.92 (17) | C41—N10—C45 | 119.7 (4) |
N2—Ni1—N1 | 70.54 (16) | C41—N10—Ni4 | 124.7 (3) |
N8—Ni1—N1 | 94.31 (15) | C45—N10—Ni4 | 115.5 (3) |
N2—Ni1—N11 | 99.85 (16) | C32—C33—C34 | 121.8 (4) |
N8—Ni1—N11 | 95.30 (15) | C32—C33—H33A | 119.1 |
N1—Ni1—N11 | 170.38 (15) | C34—C33—H33A | 119.1 |
N2—Ni1—C11 | 34.04 (15) | N1—C1—H1A | 109.5 |
N8—Ni1—C11 | 130.90 (16) | N1—C1—H1B | 109.5 |
N1—Ni1—C11 | 36.62 (15) | H1A—C1—H1B | 109.5 |
N11—Ni1—C11 | 133.77 (15) | N1—C1—H1C | 109.5 |
N2—Ni1—Ni4 | 95.25 (12) | H1A—C1—H1C | 109.5 |
N8—Ni1—Ni4 | 84.14 (12) | H1B—C1—H1C | 109.5 |
N1—Ni1—Ni4 | 108.08 (12) | N5—C4—H4A | 109.5 |
N11—Ni1—Ni4 | 72.60 (11) | N5—C4—H4B | 109.5 |
C11—Ni1—Ni4 | 106.04 (11) | H4A—C4—H4B | 109.5 |
N4—Ni2—N1 | 107.15 (16) | N5—C4—H4C | 109.5 |
N4—Ni2—N9 | 104.29 (16) | H4A—C4—H4C | 109.5 |
N1—Ni2—N9 | 101.35 (15) | H4B—C4—H4C | 109.5 |
N4—Ni2—Cl1 | 118.08 (13) | N11—C8—H8A | 109.5 |
N1—Ni2—Cl1 | 112.46 (12) | N11—C8—H8B | 109.5 |
N9—Ni2—Cl1 | 111.92 (12) | H8A—C8—H8B | 109.5 |
N3—Ni3—N5 | 109.72 (17) | N11—C8—H8C | 109.5 |
N3—Ni3—N11 | 105.25 (16) | H8A—C8—H8C | 109.5 |
N5—Ni3—N11 | 100.78 (15) | H8B—C8—H8C | 109.5 |
N3—Ni3—Cl2 | 112.30 (13) | N9—C6—H6A | 109.5 |
N5—Ni3—Cl2 | 113.00 (12) | N9—C6—H6B | 109.5 |
N11—Ni3—Cl2 | 114.95 (11) | H6A—C6—H6B | 109.5 |
N6—Ni4—N10 | 163.47 (17) | N9—C6—H6C | 109.5 |
N6—Ni4—N5 | 70.75 (17) | H6A—C6—H6C | 109.5 |
N10—Ni4—N5 | 93.34 (17) | H6B—C6—H6C | 109.5 |
N6—Ni4—N9 | 99.29 (17) | N4—C21—N6 | 118.1 (4) |
N10—Ni4—N9 | 96.68 (16) | N4—C21—C22 | 125.6 (5) |
N5—Ni4—N9 | 169.96 (16) | N6—C21—C22 | 116.3 (5) |
N6—Ni4—C25 | 34.22 (17) | C14—C13—C12 | 122.4 (4) |
N10—Ni4—C25 | 130.15 (17) | C14—C13—H13A | 118.8 |
N5—Ni4—C25 | 36.81 (16) | C12—C13—H13A | 118.8 |
N9—Ni4—C25 | 133.15 (17) | C33—C32—C31 | 118.4 (4) |
N6—Ni4—Ni1 | 95.77 (13) | C33—C32—H32A | 120.8 |
N10—Ni4—Ni1 | 84.81 (12) | C31—C32—H32A | 120.8 |
N5—Ni4—Ni1 | 108.49 (12) | C23—C22—C21 | 119.5 (5) |
N9—Ni4—Ni1 | 73.09 (11) | C23—C22—H22A | 120.3 |
C25—Ni4—Ni1 | 107.90 (12) | C21—C22—H22A | 120.3 |
C35—N9—C6 | 113.9 (3) | C43—C42—C41 | 118.7 (5) |
C35—N9—Ni4 | 112.3 (3) | C43—C42—H42A | 120.7 |
C6—N9—Ni4 | 109.5 (3) | C41—C42—H42A | 120.7 |
C35—N9—Ni2 | 108.8 (3) | N2—C11—C12 | 124.5 (4) |
C6—N9—Ni2 | 101.4 (3) | N2—C11—N1 | 105.2 (4) |
Ni4—N9—Ni2 | 110.41 (17) | C12—C11—N1 | 130.4 (5) |
C11—N1—C1 | 113.9 (4) | N2—C11—Ni1 | 52.0 (2) |
C11—N1—Ni1 | 90.1 (3) | C12—C11—Ni1 | 174.7 (4) |
C1—N1—Ni1 | 121.4 (3) | N1—C11—Ni1 | 53.3 (2) |
C11—N1—Ni2 | 113.6 (3) | C21—N4—C3 | 117.0 (4) |
C1—N1—Ni2 | 114.3 (3) | C21—N4—Ni2 | 125.9 (3) |
Ni1—N1—Ni2 | 100.99 (18) | C3—N4—Ni2 | 115.3 (3) |
C25—N6—C21 | 122.2 (4) | N6—C25—C24 | 123.7 (5) |
C25—N6—Ni4 | 93.4 (3) | N6—C25—N5 | 105.7 (4) |
C21—N6—Ni4 | 144.3 (3) | C24—C25—N5 | 130.7 (5) |
C45—N11—C8 | 114.4 (4) | N6—C25—Ni4 | 52.4 (2) |
C45—N11—Ni1 | 115.0 (3) | C24—C25—Ni4 | 172.7 (4) |
C8—N11—Ni1 | 108.9 (3) | N5—C25—Ni4 | 53.8 (2) |
C45—N11—Ni3 | 107.2 (3) | C13—C14—C15 | 121.0 (5) |
C8—N11—Ni3 | 101.1 (3) | C13—C14—H14A | 119.5 |
Ni1—N11—Ni3 | 109.33 (17) | C15—C14—H14A | 119.5 |
C31—N8—C35 | 119.0 (4) | N7—C5—H5A | 109.5 |
C31—N8—Ni1 | 124.4 (3) | N7—C5—H5B | 109.5 |
C35—N8—Ni1 | 116.3 (3) | H5A—C5—H5B | 109.5 |
C25—N5—C4 | 114.5 (4) | N7—C5—H5C | 109.5 |
C25—N5—Ni4 | 89.4 (3) | H5A—C5—H5C | 109.5 |
C4—N5—Ni4 | 121.4 (3) | H5B—C5—H5C | 109.5 |
C25—N5—Ni3 | 115.3 (3) | N3—C2—H2A | 109.5 |
C4—N5—Ni3 | 113.3 (3) | N3—C2—H2B | 109.5 |
Ni4—N5—Ni3 | 100.52 (17) | H2A—C2—H2B | 109.5 |
C11—C12—C13 | 114.9 (5) | N3—C2—H2C | 109.5 |
C11—C12—H12A | 122.5 | H2A—C2—H2C | 109.5 |
C13—C12—H12A | 122.5 | H2B—C2—H2C | 109.5 |
N10—C45—N11 | 114.7 (4) | C22—C23—C24 | 122.9 (5) |
N10—C45—C44 | 120.3 (4) | C22—C23—H23A | 118.5 |
N11—C45—C44 | 125.0 (4) | C24—C23—H23A | 118.5 |
N8—C35—C34 | 121.2 (4) | C43—C44—C45 | 118.6 (5) |
N8—C35—N9 | 113.5 (4) | C43—C44—H44A | 120.7 |
C34—C35—N9 | 125.3 (4) | C45—C44—H44A | 120.7 |
C15—N3—C2 | 115.2 (4) | C25—C24—C23 | 115.1 (5) |
C15—N3—Ni3 | 124.9 (3) | C25—C24—H24A | 122.4 |
C2—N3—Ni3 | 117.8 (3) | C23—C24—H24A | 122.4 |
N10—C41—N12 | 114.9 (5) | N12—C7—H7B | 109.5 |
N10—C41—C42 | 121.7 (5) | N12—C7—H7C | 109.5 |
N12—C41—C42 | 123.3 (5) | H7B—C7—H7C | 109.5 |
N3—C15—N2 | 117.3 (4) | N12—C7—H7D | 109.5 |
N3—C15—C14 | 127.3 (4) | H7B—C7—H7D | 109.5 |
N2—C15—C14 | 115.4 (5) | H7C—C7—H7D | 109.5 |
N7—C31—N8 | 116.9 (4) | C41—N12—C7 | 123.4 (5) |
N7—C31—C32 | 122.4 (4) | C41—N12—H12B | 118.3 |
N8—C31—C32 | 120.8 (4) | C7—N12—H12B | 118.3 |
C35—C34—C33 | 118.6 (4) | N4—C3—H3A | 109.5 |
C35—C34—H34A | 120.7 | N4—C3—H3B | 109.5 |
C33—C34—H34A | 120.7 | H3A—C3—H3B | 109.5 |
C31—N7—C5 | 123.3 (4) | N4—C3—H3C | 109.5 |
C31—N7—H7A | 118.4 | H3A—C3—H3C | 109.5 |
C5—N7—H7A | 118.4 | H3B—C3—H3C | 109.5 |
C11—N2—C15 | 121.6 (4) | C42—C43—C44 | 120.8 (5) |
C11—N2—Ni1 | 93.9 (3) | C42—C43—H43A | 119.6 |
C15—N2—Ni1 | 144.4 (4) | C44—C43—H43A | 119.6 |
Experimental details
Crystal data | |
Chemical formula | [Ni4(C7H9N3)2(C7H10N3)2Cl2] |
Mr | 848.44 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 213 |
a, b, c (Å) | 12.710 (7), 10.903 (6), 24.729 (14) |
β (°) | 99.842 (11) |
V (Å3) | 3376 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.40 |
Crystal size (mm) | 0.38 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART 1000 area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.463, 0.796 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16834, 5894, 4026 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.094, 1.08 |
No. of reflections | 5894 |
No. of parameters | 415 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.66, −0.58 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.
Ni1—N2 | 1.891 (4) | Ni3—N3 | 1.929 (4) |
Ni1—N8 | 1.904 (4) | Ni3—N5 | 2.012 (4) |
Ni1—N1 | 1.919 (4) | Ni3—N11 | 2.059 (4) |
Ni1—N11 | 1.957 (4) | Ni3—Cl2 | 2.2492 (18) |
Ni2—N4 | 1.945 (4) | Ni4—N6 | 1.885 (4) |
Ni2—N1 | 2.000 (4) | Ni4—N10 | 1.913 (4) |
Ni2—N9 | 2.056 (4) | Ni4—N5 | 1.915 (4) |
Ni2—Cl1 | 2.2369 (17) | Ni4—N9 | 1.948 (4) |
Molecules in the title complex, (I) (Fig. 1), are non-centrosymmetic but the crystals are racemic. During the reaction, two equivalents of the organic amine were fully deprotonated forming dianions and two equivalents were only partially deprotonated giving monoanions. In this tetranuclear complex, there are four divalent Ni atoms. Two of them, Ni1 and Ni4, are square planar and bonded to four N donors while the others, Ni2 and Ni3, are in a distorted tetrahedral geometry, with three coordination sites occupied by N donors and the fourth one by a Cl atom (Table 1). Even though there are a series of compounds having three Ni atoms forming a linear chain that have both four-coordinate and five-coordinate metal atoms (Clérac et al., 1999; Cotton et al., 2001, 2006), examples of clusters having four Ni atoms in a four-coordinate environment but two different geometries are rare.